Stable Ni Isotope Fractionation In Systems Relevant To Banded Iron-Formations

An important event in the evolution of life was the rise of atmospheric oxygen during the Proterozoic. Preceding the rise in O2 was a decline in atmospheric methane concentrations, likely due to decreased productivity of methanogenic Archaea. Based on Ni concentrations in banded iron formations (BIF), Konhauser et al. (2009) hypothesized that mantle cooling during the Archaean reduced the amount of Ni present in igneous rocks and in oceans, causing a Ni shortage for methanogens. Methanogens use Ni for cofactor F430, a catalyst during methanogenesis. To confirm Konhauser's hypothesis, a proxy for methanogen productivity in the rock record is necessary, in order to determine whether a decline in methanogen populations correlated with the observed decrease in maximum Ni contents in rocks from the Archaean. Ni isotope ratios recorded in BIF (oceanic sediments consisting of layered iron oxides and cherts) may provide evidence of a decline in methane production. Cameron et al. (2009) have shown that methanogens preferentially assimilate light Ni isotopes. Thus Ni isotopes in BIF have potential use as biomarkers for methanogenesis. Ferrihydrite was almost certainly the dominant Fe-oxide phase precipitating during BIF deposition. Ferrihydrite nanoparticles have large surface areas and are able to remove aqueous metals from solution through multiple sorption mechanisms. Thus we investigated experimentally the relationship between Ni isotopes in solution and Ni associated with ferrihydrite. We experimented with two different sorption mechanisms: adsorption of aqueous Ni onto surfaces of synthetic ferrihydrite and coprecipitation of aqueous Ni with ferrihydrite. Preliminary results indicate that light isotopes are preferentially associated with ferrihydrite in both adsorption and coprecipitation experiments, with an average fractionation of 0.3‰ in terms of δ60/58 Ni. Future experiments will investigate whether the observed isotope fractionations reflect kinetics or equilibrium, thus determining whether or not authigenic ferrihydrite incorporates a straightforward record of Ni isotopes from the water mass. Konhauser et al. (2009) Nature 480, 750. Cameron et al. (2009) PNAS 106, 10944.